EP4051750A1 - Fluides caloporteurs pour utilisation dans des applications de refroidisseur à basse température - Google Patents

Fluides caloporteurs pour utilisation dans des applications de refroidisseur à basse température

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Publication number
EP4051750A1
EP4051750A1 EP20811169.0A EP20811169A EP4051750A1 EP 4051750 A1 EP4051750 A1 EP 4051750A1 EP 20811169 A EP20811169 A EP 20811169A EP 4051750 A1 EP4051750 A1 EP 4051750A1
Authority
EP
European Patent Office
Prior art keywords
composition
weight percent
hfe
hydrofluoroether
heat transfer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20811169.0A
Other languages
German (de)
English (en)
Inventor
Harrison K. Musyimi
Raymond Wu
Michael R. Fraser
Luke David SIMONI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemours Co FC LLC
Original Assignee
Chemours Co FC LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemours Co FC LLC filed Critical Chemours Co FC LLC
Publication of EP4051750A1 publication Critical patent/EP4051750A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
    • F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
    • F25B9/006—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant the refrigerant containing more than one component
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/11—Ethers
    • C09K2205/112—Halogenated ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/128—Perfluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40—Replacement mixtures

Definitions

  • compositions e.g, heat transfer fluids
  • the present application relates to compositions (e.g, heat transfer fluids) for use in refrigeration and heat transfer applications.
  • the compositions of the present invention are useful in methods for producing cooling and heating, and methods for replacing refrigerants and refrigeration, air conditioning, and heat pump apparatuses.
  • PFCs Perfluorocarbons
  • compositions comprising:
  • the present application further provides processes for producing cooling, comprising condensing a composition provided herein, and thereafter evaporating said composition in the vicinity of a body to be cooled.
  • the present application further provides methods of using a composition provided herein as a heat transfer fluid, wherein the heat transfer fluid is a working fluid that removes heat from, adds heat to, or maintains temperature of the vicinity of a body to be cooled or heated.
  • the heat transfer fluid is a working fluid that removes heat from, adds heat to, or maintains temperature of the vicinity of a body to be cooled or heated.
  • the present application further provides methods of replacing a heat transfer fluid in a cooling fluid distribution unit, refrigeration or heat pump system, comprising providing a composition provided herein as replacement for said heat transfer fluid.
  • the present application further provides refrigeration systems (e.g., ultra-low temperature refrigeration or chiller systems), comprising a composition provided herein.
  • refrigeration systems e.g., ultra-low temperature refrigeration or chiller systems
  • FIG. 1 shows the calculated solid-liquid equilibria of a blend of 70 wt% MPHE/30 wt% HFE-7200 over the entire composition range of the mixture.
  • FIG. 2 shows a comparison of the absolute viscosity of pure MPHE and a blend of 70 wt% MPHE/30 wt% HFE-7200.
  • FIG. 3 shows the calculated solid-liquid equilibria of a blend of MPHE and VertrelTM XF over the entire composition range.
  • FIG. 4 shows the calculated solid-liquid equilibria of a blend of MPHE and DR CFX70 over the entire composition range.
  • FIG. 5 shows the calculated solid-liquid equilibria a blend of HFE-7500/HFE-7000 over the entire composition range of the mixture.
  • MPHE methyl perfluoroheptene ether
  • Chiller heat transfer fluid or circulating fluid can remove heat, add heat or maintain a temperature through chiller’s refrigeration circuits.
  • the operating temperature can be, for example, between -80°C and +60°C.
  • a heat transfer fluid it may also be necessary for a heat transfer fluid to be pumpable (e.g. , viscosity at about 10 cSt or less) at temperatures below -95°C (e.g., to maintain consistent a temperature at -80°) while maintaining heat transfer, dielectric, and fluid properties.
  • the chiller’s refrigeration cycles start with a low-pressure liquid entering the evaporator/heat exchanger.
  • the heat from the heat transfer fluid boils the refrigerant, which change the refrigerant from a low-pressure liquid to a low-pressure gas, and the low-pressure gas enters the compressor where it is compressed to high-pressure gas.
  • the high-pressure gas enters the condenser where ambient air or cooling water removes heat to cool it to a high- pressure liquid.
  • the high-pressure liquid travels to the expansion valve, when the heat transfer fluid temperature is rising higher than the set temperature, the expansion valve will open to introduce refrigerant at a lower temperature to the heat exchanger. With this, the heat transfer fluid will be cooled to the desired temperature.
  • Ultra-low temperature refrigeration circuits may be useful, for example, in the following applications:
  • Medical applications uses in maintaining temperature for medical imaging instrumentation (e.g, X-ray imaging, magnetic resonance imaging (MRI), and the like) and/or blood or other biological sample or tissue preservation equipment.
  • medical imaging instrumentation e.g, X-ray imaging, magnetic resonance imaging (MRI), and the like
  • blood or other biological sample or tissue preservation equipment e.g., X-ray imaging, magnetic resonance imaging (MRI), and the like
  • Machine tooling applications uses in maintaining temperature for wire cutting, plasma welding, laser machining, and the like.
  • Analytical equipment applications uses in maintaining temperature of electron microscopes (e.g., scanning electronic microscopes, transmissions electron microscopes, and the like), gas chromatographs (GC), X-ray analytical instruments, and the like.
  • electron microscopes e.g., scanning electronic microscopes, transmissions electron microscopes, and the like
  • GC gas chromatographs
  • X-ray analytical instruments e.g., X-ray analytical instruments, and the like.
  • the present application provides new compositions that may be useful as heat transfer fluids over large temperature ranges and may be particularly useful in ultra-low temperature refrigeration applications as described herein.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • the term “consisting essentially of’ is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention.
  • the term “consists essentially of’ or “consisting essentially of’ occupies a middle ground between “comprising” and “consisting of’.
  • Global warming potential is an index for estimating relative global warming contribution due to atmospheric emission of a kilogram of a particular greenhouse gas compared to emission of a kilogram of carbon dioxide. GWP can be calculated for different time horizons showing the effect of atmospheric lifetime for a given gas. The GWP for the 100-year time horizon is commonly the value referenced.
  • ODP Ozone depletion potential
  • Refrigeration capacity (sometimes referred to as cooling capacity) is a term to define the change in enthalpy of a refrigerant or working fluid in an evaporator per unit mass of refrigerant or working fluid circulated.
  • Volumetric cooling capacity refers to the amount of heat removed by the refrigerant or working fluid in the evaporator per unit volume of refrigerant vapor exiting the evaporator.
  • the refrigeration capacity is a measure of the ability of a refrigerant, working fluid or heat transfer composition to produce cooling. Therefore, the higher the volumetric cooling capacity of the working fluid, the greater the cooling rate that can be produced at the evaporator with the maximum volumetric flow rate achievable with a given compressor. Cooling rate refers to the heat removed by the refrigerant in the evaporator per unit time.
  • volumetric heating capacity is a term to define the amount of heat supplied by the refrigerant or working fluid in the condenser per unit volume of refrigerant or working fluid vapor entering the compressor. The higher the volumetric heating capacity of the refrigerant or working fluid, the greater the heating rate that is produced at the condenser with the maximum volumetric flow rate achievable with a given compressor.
  • Coefficient of performance is the amount of heat removed in the evaporator divided by the energy required to operate the compressor. The higher the COP, the higher the energy efficiency. COP is directly related to the energy efficiency ratio (EER), that is, the efficiency rating for refrigeration or air conditioning equipment at a specific set of internal and external temperatures.
  • EER energy efficiency ratio
  • a heat transfer medium comprises a composition used to carry heat from a heat source to a heat sink. For example, heat from a body to be cooled to a chiller evaporator or from a chiller condenser to a cooling tower or other configuration where heat can be rejected to the ambient.
  • a working fluid or refrigerant comprises a compound or mixture of compounds (e.g., a composition provided herein) that function to transfer heat in a cycle wherein the working fluid undergoes a phase change from a liquid to a gas and back to a liquid in a repeating cycle.
  • a compound or mixture of compounds e.g., a composition provided herein
  • Subcooling is the reduction of the temperature of a liquid below that liquid's saturation point for a given pressure.
  • the saturation point is the temperature at which a vapor composition is completely condensed to a liquid (also referred to as the bubble point). But subcooling continues to cool the liquid to a lower temperature liquid at the given pressure. By cooling a liquid below the saturation temperature, the net refrigeration capacity can be increased. Subcooling thereby improves refrigeration capacity and energy efficiency of a system.
  • Subcool amount is the amount of cooling below the saturation temperature (in degrees) or how far below its saturation temperature a liquid composition is cooled.
  • Saturation vapor temperature is the temperature at which, if a vapor composition is cooled, the first drop of liquid is formed, also referred to as the “dew point”.
  • the term “substantially free” refers to less than about 1%, e.g., less than about 0.5%, less than about 0.25%, less than about 0.1%, less than about 0.01%, less than about 0.001%, less than about 0.0001%, less than about 0.00001%, and the like.
  • CAP cooling (or heating) capacity
  • COP coefficient of performance
  • cSt or CSt
  • DR CFX70 tetradecafluoroheptene (boiling point: 71.5°C; MW: 350 g/mol)
  • FC77 or FluorinertTM Electronic Liquid FC-77 thermally stable, fully -fluorinated liquid (primarily compounds with 8 carbon; commercially available from 3M).
  • HFE hydrofluoroether
  • HFE-7000 1-methoxyheptafluoropropane
  • HFE-7100 mixture of methyl nonafluorobutyl ether and methyl nonfluoroisobutyl ether
  • HFE-7200 or HFE-569mccc mixture of 1 -ethoxy perfluorobutane and 1 -ethoxy perfluoro-isobutane
  • HFE-7500 2-(trifluoromethyl)-3-ethoxydodecafluorohexane
  • HFT heat transfer fluid HT110 or Galden® HT-110: 1-propene 1,1,2,3,3,3-hexafluoro- oxidized, polymerized.
  • MPHE methyl perfluoroheptene ether
  • ODP ozone depletion potential
  • PFC perfluorocarbon
  • VertrelTM XF or HFC-43-10mee 1,1,1,2,2,3,4,5,5,5-decafluoropentane wt%: weight percent
  • compositions compnsing The present application provides compositions compnsing:
  • the composition exhibits a maximum kinematic viscosity of about 10 cSt or less, for example, about 9 cSt or less, about 8 cSt or less, about 7 cSt or less about 6 cSt or less, about 5 cSt or less, about 4 cSt or less, about 3 cSt or less, about 2 cSt or less, or about 1 cSt or less. In some embodiments, the composition exhibits a maximum kinematic viscosity of about 6 cSt or less.
  • the composition exhibits a maximum kinematic viscosity of about 10 cSt or less at a temperature of about -90°C to about -100°C, for example, about 8 cSt or less, about 6 cSt or less, about 4 cSt or less, about 2 cSt or less, or about 1 cSt or less at a temperature of about -90°C to about -100°C. In some embodiments, the composition exhibits a maximum kinematic viscosity of about 6 cSt or less at a temperature of about -90°C to about -100°C.
  • the composition exhibits a maximum kinematic viscosity of about 0.1 cSt to about 10 cSt, for example, about 0.1 cSt to about 8 cSt, about 0.1 cSt to about 6 cSt, about 0.1 cSt to about 4 cSt, about 0.1 cSt to about 2 cSt, about 0.1 cSt to about 1 cSt, about 1 cSt to about 10 cSt, about 1 cSt to about 8 cSt, about 1 cSt to about 6 cSt, about 1 cSt to about 4 cSt about 1 cSt to about 2 cSt, about 2 cSt to about 10 cSt, about 2 cSt to about 8 cSt, about 2 cSt to about 6 cSt, about 2 cSt to about 4 cSt, about 4 cSt to about 10 cSt, about 4 cSt
  • the composition exhibits a maximum kinematic viscosity of about 0.1 cSt to about 10 cSt at a temperature of about -90°C to about -100°C, for example, about 0.1 cSt to about 8 cSt, about 0.1 cSt to about 6 cSt, about 0.1 cSt to about 4 cSt, about 0.1 cSt to about 2 cSt, about 0.1 cSt to about 1 cSt, about 1 cSt to about 10 cSt, about 1 cSt to about 8 cSt, about 1 cSt to about 6 cSt, about 1 cSt to about 4 cSt, about 1 cSt to about 2 cSt, about 2 cSt to about 10 cSt, about 2 cSt to about 8 cSt, about 2 cSt to about 6 cSt, about 2 cSt to about 4 cSt, about
  • the composition is non-flammable.
  • the composition comprises about 15 to about 95 weight percent alkyl perfluoroalkene ether, for example, about 15 to about 90, about 15 to about 80, about 15 to about 70, about 15 to about 60, about 15 to about 50, about 15 to about 40, about 15 to about 30, about 15 to about 20, about 20 to about 95, about 20 to about 90, about 20 to about 80, about 20 to about 70, about 20 to about 60, about 20 to about 50, about 20 to about 40, about 20 to about 30, about 30 to about 95, about 30 to about 90, about 30 to about 80, about 30 to about 70, about 30 to about 60, about 30 to about 50, about 30 to about 40, about 40 to about 95, about 40 to about 90, about 40 to about 80, about 40 to about 70, about 40 to about 60, about 40 to about 50, about 50 to about 95, about 50 to about 90, about 50 to about 80, about 50 to about 70, about 50 to about 60, about 60 to about 95, about 60 to about 90, about 60 to about 80, about 60 to about 70, about 50 to
  • the composition comprises about 60 to about 90 weight percent alkyl perfluoroalkene ether. In some embodiments, the composition comprises about 60 to about 80 weight percent alky l perfluoroalkene ether. In some embodiments, the composition comprises about 65 to about 75 weight percent alkyl perfluoroalkene ether. In some embodiments, the composition comprises about 70 weight percent alkyl perfluoroalkene ether. In some embodiments, the composition comprises about 5 to about
  • the composition comprises about 10 weight percent alkyl perfluoroalkene ether.
  • the alkyl perfluoroalkene ether is methyl perfluoroheptene ether. In some embodiments, the methyl perfluoroheptene ether comprises a mixture of two or more structural and/or stereoisomers.
  • the methyl perfluoroheptene ether comprises a mixture of about 48 to about 52 weight percent 5-methoxy perfluoro-3-heptene, about 18 to about 22 weight percent 3-methoxy perfluoro-3-heptene, about 18 to about 22 weight percent 4- methoxy perfluoro-2-heptene, and about 6 to about 10 weight percent 4-methoxy perfluoro-3 -heptene.
  • the methyl perfluoroheptene ether comprises a mixture of about 50 weight percent 5-methoxy perfluoro-3 -heptene, about 20 weight percent 3- methoxy perfluoro-3-heptene, about 20 weight percent 4-methoxy perfluoro-2-heptene, and about 8 weight percent 4-methoxy perfluoro-3-heptene.
  • the methyl perfluoroheptene ether comprises a mixture of about 48 to about 52 weight percent 5-methoxy (E)-perfluoro-3-heptene, about 12 to about
  • the methyl perfluoroheptene ether comprises a mixture of about 50 weight percent 5-methoxy (E)-perfluoro-3 -heptene, about 14 weight percent 3- methoxy (E)-perfluoro-3-heptene, about 6 weight percent 3-methoxy (Z)-perfluoro-3- heptene, about 20 weight percent 4-methoxy (E)-perfluoro-2-heptene, about 2 weight percent 4-methoxy (Z)-perfluoro-3-heptene, and about 6 weight percent 4-methoxy (E)- perfluoro-3 -heptene.
  • the composition comprises:
  • an alkyl perfluoroalkene ether (i) an alkyl perfluoroalkene ether; and (ii) a compound selected from a second hydrofluoroether. a peril uorocarbon. and a perfluoropolyether.
  • the composition comprises an alkyl perfluoroalkene ether and a second hydrofluoroether. In some embodiments, the composition comprises methyl perfluoroheptene ether and a second hydrofluoroether.
  • the composition comprises about 5 to about 85 weight percent of the second hydrofluoroether, for example, about 5 to about 80, about 5 to about 70, about 5 to about 60, about 5 to about 50, about 5 to about 40, about 5 to about 30, about 5 to about 20, about 5 to about 10, about 10 to about 85, about 10 to about 80, about 10 to about 70, about 10 to about 60, about 10 to about 50, about 10 to about 40, about 10 to about 30, about 10 to about 20, about 20 to about 85, about 20 to about 80, about 20 to about 70, about 20 to about 60, about 20 to about 50, about 20 to about 40, about 20 to about 30, about 30 to about 85, about 30 to about 80, about 30 to about 70, about 30 to about 60, about 30 to about 50, about 30 to about 40, about 40 to about 85, about 40 to about 80, about 40 to about 70, about 40 to about 60, about 40 to about 50, about 50 to about 85, about 50 to about 80, about 50 to about 70, about 50 to about 60, about 60 to about 85, about 50 to about
  • the composition comprises about 10 to about 40 weight percent of the second hydrofluoroether. In some embodiments, the composition compnses about 20 to about 40 weight percent of the second hydrofluoroether. In some embodiments, the composition comprises about 25 to about 35 weight percent of the second hydrofluoroether. In some embodiments, the composition comprises about 30 weight percent of the second hydrofluoroether.
  • the second hydrofluoroether is selected from HFE-7000, HFE-7100, FIFE-7200, and FIFE-7500. In some embodiments, the second hydrofluoroether is HFE-7000. In some embodiments, the second hydrofluoroether is HFE-7100. In some embodiments, the second hydrofluoroether is HFE-7200. In some embodiments, the second hydrofluoroether is HFE-7500.
  • composition comprises methyl perfluoroheptene ether and HFE-7200. In some embodiments, composition comprises about 60 to about 80 weight percent methyl perfluoroheptene ether and about 40 to about 20 weight percent HFE-7200. In some embodiments, composition comprises about 65 to about 75 weight percent methyl perfluoroheptene ether and about 35 to about 25 weight percent HFE-7200. In some embodiments, the composition comprises about 70 weight percent methyl perfluoroheptene ether and about 30 weight percent HFE-7200.
  • the composition comprises an alkyl perfluoroalkene ether and a perfluorocarbon. In some embodiments, the composition comprises methyl perfluoroheptene ether and a perfluorocarbon.
  • the composition comprises about 15 to about 5 weight percent of the perfluorocarbon, for example, about 15 to about 10 or about 10 to about 5 weight percent of the perfluorocarbon. In some embodiments, the composition comprises about 10 weight percent of the perfluorocarbon. In some embodiments, the perfluorocarbon is FC77.
  • FC77 refers to FluorinertTM Electronic Liquid FC-77, which is commercially available from 3M and would be readily understood by a skilled artisan.
  • FC77 Physical properties of FC77 are provided below. Additional information can be found, for example, in the Product Information Sheet from 3M, the disclosure of which is incorporated herein by reference in its entirety. Appearance Clear, colorless
  • the composition comprises about 85 to about 95 weight percent methyl perfluoroheptene ether and about 15 to about 5 weight percent FC77. In some embodiments, the composition comprises about 90 weight percent methyl perfluoroheptene ether and about 10 weight percent FC77. In some embodiments, the composition comprises an alkyl perfluoroalkene ether and a perfluoropoly ether. In some embodiments, the composition comprises methyl perfluoroheptene ether and a perfluoropoly ether.
  • the composition comprises about 15 to about 5 weight percent of the perfluoropoly ether, for example, about 15 to about 10 or about 10 to about 5 weight percent of the perfluoropoly ether. In some embodiments, the composition comprises about 10 weight percent of the perfluoropolyether. In some embodiments, the perfluoropoly ether is HT110.
  • HT110 refers to Galden® HT-110 (1-propene 1, 1,2, 3,3,3- hexafluoro- oxidized, polymerized), which is commercially available from Solvay and would be readily understood by a skilled artisan. Physical properties of HT110 are provided below.
  • the composition comprises about 85 to about 95 weight percent methyl perfluoroheptene ether and about 15 to about 5 weight percent HT110. In some embodiments, the composition comprises about 90 weight percent methyl perfluoroheptene ether and about 10 weight percent HT110.
  • the composition comprises:
  • the composition comprises about 70 to about 90 weight percent of the first hydrofluoroether, for example, about 70 to about 85, about 70 to about 80, about 70 to about 75, about 75 to about 90, about 75 to about 85, about 75 to about 80, about 80 to about 90, about 80 to about 85, or about 85 to about 90 weight percent of the first hydrofluoroether.
  • the first hydrofluoroether is HFE-7500.
  • the composition comprises about 30 to about 10 weight percent of the second hydrofluoroether, for example, about 30 to about 15, about 30 to about 20, about 30 to about 25, about 25 to about 10, about 25 to about 15, about 25 to about 20, about 20 to about 10, about 20 to about 15, or about 15 to about 10 weight percent of the second hydrofluoroether.
  • the composition comprises about 70 to about 90 weight percent of the first hydrofluoroether and about 30 to about 10 weight percent of the second hydrofluoroether.
  • the composition comprises about 80 weight percent of the first hydrofluoroether and about 20 weight percent of the second hydrofluoroether.
  • the composition comprises about 70 to about 90 weight percent HFE-7500 and about 30 to about 10 weight percent of the second hydrofluoroether. In some embodiments, the composition comprises about 80 weight percent HFE-7500 and about 20 weight percent of the second hydrofluoroether.
  • the second hydrofluoroether is selected from HFE-7000, HFE-7100, and HFE-7200. In some embodiments, the second hydrofluoroether is HFE- 7000. In some embodiments, the second hydrofluoroether is HFE-7100. In some embodiments, the second hydrofluoroether is HFE-7200.
  • compositions provided herein can act as a working fluid used to carry heat from a heat source to a heat sink.
  • Such heat transfer compositions may also be useful as a refrigerant in a cycle wherein the fluid undergoes a phase change; that is, from a liquid to a gas and back, or vice versa, or as a single phase working fluid (e.g., as a Chiller heat transfer fluid (HFT) or circulating fluid).
  • HFT Chiller heat transfer fluid
  • Examples of heat transfer systems include but are not limited to air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, high temperature heat pumps, mobile refrigerators, mobile air conditioning units, immersion cooling systems, data-center cooling systems, and combinations thereof.
  • the exemplary heat transfer systems can comprise components useful for single phase heat transfer.
  • the present application provides heat transfer systems (e.g., a heat transfer apparatus) as described herein, comprising a composition provided herein.
  • the composition provided herein is useful as a working fluid or heat transfer fluid (e.g., a working fluid for refrigeration or heating applications) in the heat transfer system.
  • the compositions provided herein are useful in an apparatus or system comprising a high temperature heat pump (e.g, a heat pump comprising a heat exchanger operating at a temperature greater than about 50°C).
  • the high temperature heat pump comprises a centrifugal compressor.
  • compositions provided herein are useful in an apparatus or system comprising a chiller apparatus. In some embodiments, the compositions provided herein are useful in an apparatus or system comprising a centrifugal chiller apparatus. In some embodiments, the compositions provided herein are useful in a centrifugal high temperature heat pump.
  • the compositions provided may be useful as a heat transfer fluid (e.g. , a chiller heat transfer fluid or circulating fluid).
  • a heat transfer fluid HFT
  • circulating fluid is a working fluid that can remove heat, add heat, or maintain a temperature through in the vicinity of a body to be cooled (e.g. , a chiller’s refrigeration circuits).
  • a pumping system circulates cool heat transfer fluid from the chiller to the process (or, e.g., semiconductor manufacturing tools). The heat transfer fluid removes heat from the process and the warmed heat transfer fluid returns to the chiller’s tank via a heat exchanger.
  • the heat transfer fluid is re-cooled at the heat exchanger and circulated back to the process side where it will again acquire heat.
  • the process requires temperature control and the circulating fluid is required to be remain in a single phase over the entire process temperature range.
  • the properties of the fluid e.g., viscosity, boiling point, and the like
  • the compositions provided herein are useful as heat transfer fluids, wherein the composition maintains a single phase (e.g., liquid) over the operating temperature range of the heat transfer system (e.g, about -140°C to about 120°C).
  • Mechanical vapor-compression refrigeration, air conditioning and heat pump systems include an evaporator, a compressor, a condenser, and an expansion device.
  • a refrigeration cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step.
  • a multiphase cycle e.g. , condensation/evaporation
  • Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in the evaporator, by withdrawing heat from the environment, at a low temperature to form a gas and produce cooling.
  • air or a heat transfer fluid flows over or around the evaporator to transfer the cooling effect caused by the evaporation of the refrigerant in the evaporator to a body to be cooled.
  • the low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature.
  • the higher-pressure (compressed) gaseous refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment.
  • the refrigerant returns to the expansion device through which the liquid expands from the higher-pressure level in the condenser to the low-pressure level in the evaporator thus repeating the cycle.
  • a body to be cooled or heated may be defined as any space, location, object or body for which it is desirable to provide cooling or heating. Examples include spaces (open or enclosed) requiring air conditioning, cooling, or heating, such as a room, an apartment, or building, such as an apartment building, university dormitory, townhouse, or other attached house or single-family home, hospitals, office buildings, supermarkets, college or university classrooms or administration buildings and automobile or truck passenger compartments. Additionally, a body to be cooled may include electronic devices, such as computer equipment, central processing units (cpu), data-centers, server banks, and personal computers among others.
  • cpu central processing units
  • in the vicinity of is meant that the evaporator of the system containing the refrigerant is located either within or adjacent to the body to be cooled, such that air moving over the evaporator would move into or around the body to be cooled.
  • in the vicinity of means that the condenser of the system containing the refrigerant is located either within or adjacent to the body to be heated, such that the air moving over the evaporator would move into or around the body to be heated.
  • in the vicinity of’ may mean that the body to be cooled is immersed directly in the heat transfer composition or tubes containing heat transfer compositions run into around internally, and out of electronic equipment, for instance.
  • Exemplary refrigeration systems include, but are not limited to, equipment including commercial, industrial or residential refrigerators and freezers, ice machines, self- contained coolers and freezers, vending machines, flooded evaporator chillers, direct expansion chillers, w3 ⁇ 4ter chiller, centrifugal chillers, walk-in and reach-in coolers and freezers, and combination systems.
  • the compositions provided herein may be used in supermarket refrigeration systems.
  • stationary applications may utilize a secondary loop system that uses a primary refrigerant to produce cooling in one location that is transferred to a remote location via a secondary heat transfer fluid.
  • the compositions provided herein are useful in single phase chiller systems (e.g, a chiller capable of operating using a single-phase heat transfer composition).
  • the single-phase chiller system comprises a single phase semi-conductor chiller.
  • the compositions provided herein are useful over a wide range of temperatures for cooling and heating applications.
  • the compositions provided herein may be suitable as a working fluid at a temperature of from about -140°C to about 120°C, for example, about -140°C to about 110°C, about -140°C to about 100°C, about -140°C to about 50°C, about -140°C to about 25°C, about -140°C to about 0°C, about -140°C to about -25°C, about -140°C to about - 50°C, about -140°C to about -100°C, about -140°C to about -120°C, about -120°C to about
  • the compositions provided herein may be suitable as a working fluid at a temperature of from -135°C to about 110°C. In some embodiments, the compositions provided herein may be suitable as a working fluid at a temperature of from -95°C to about 100°C. In some embodiments, the compositions provided herein may be suitable as a working fluid at a temperature of from -70°C to about 60°C.
  • compositions provided herein are useful in mobile heat transfer systems, including refrigeration, air conditioning, or heat pump systems or apparatus. In some embodiments, the compositions are useful in stationary heat transfer systems, including refrigeration, air conditioning, or heat pump systems or apparatus.
  • mobile refrigeration, air conditioning, or heat pump systems refers to any refrigeration, air conditioner, or heat pump apparatus incorporated into a transportation unit for the road, rail, sea or air.
  • Mobile air conditioning or heat pumps systems may be used in automobiles, trucks, railcars or other transportation systems.
  • Mobile refrigeration may include transport refrigeration in trucks, airplanes, or rail cars.
  • apparatus which are meant to provide refrigeration for a system independent of any moving carrier known as “intermodal” systems, are including in the present inventions.
  • intermodal systems include '' containers (combined sea'land transport) as well as “swap bodies” (combined road and rail transport).
  • stationary air conditioning or heat pump systems are systems that are fixed in place during operation.
  • a stationary air conditioning or heat pump system may be associated within or attached to buildings of any variety.
  • These stationar applications may be stationary air conditioning and heat pumps, including but not limited to chillers, heat pumps, including residential and high temperature heat pumps, residential, commercial or industrial air conditioning systems, and including window, ductless, ducted, packaged terminal, and those exterior but connected to the building such as rooftop systems.
  • Stationary heat transfer may refer to systems for cooling electronic devices, such as immersion cooling systems, submersion cooling systems, phase change cooling systems, data-center cooling systems or simply liquid cooling systems.
  • a method for using the present compositions as a heat transfer fluid. The method comprises transporting said composition from a heat source to a heat sink.
  • a method for producing cooling comprising evaporating any of the present compounds or compositions in the vicinity of a body to be cooled, and thereafter condensing said composition.
  • a method for producing heating comprising condensing any of the present compositions in the vicinity of a body to be heated, and thereafter evaporating said compositions.
  • the composition is for use in heat transfer, wherein the working fluid is a heat transfer component.
  • compositions of the invention are for use in refrigeration or air conditioning.
  • compositions of the present invention may be useful for reducing or eliminating the flammability of flammable refrigerants provided herein.
  • the present application provided herein is a method for reducing the flammability of a flammable refrigerant comprising adding a composition comprising a composition as disclosed herein to a flammable refrigerant.
  • compositions provided herein may be useful as a replacement for a currently used (“incumbent”) refrigerant or oil.
  • incumbent refrigerant or “incumbent oil” shall be understood to mean the refrigerant or oil for which the heat transfer system was designed to operate, or the refrigerant or oil that is resident in the heat transfer system.
  • the compositions provided herein may be useful as a replacement for an incumbent refrigerant selected from perfluorocarbon, a perfluoropolyether, a silicon oil, a hydrocarbon oil, and an ethylene glycol aqueous solution.
  • the replacement composition i.e., the composition provided herein
  • increases the operating temperature range of the refrigeration or heat pump system compared to the heat transfer fluid e.g., increases the operating temperature to a temperature of from about -140°C to about 120°C, as described herein).
  • replacement refrigerants are most useful if capable of being used in the original refrigeration equipment designed for a different refrigerant, e.g., with minimal to no system modifications.
  • some embodiments of the disclosed compositions are useful as refrigerants and provide at least comparable cooling performance (meaning cooling capacity) as the refrigerant for which a replacement is being sought.
  • the high temperature heat pump comprises a condenser operating at a temperature greater than about 50°C. In some embodiments, the high temperature heat pump comprises a condenser operating at a temperature greater than about 100°C. In some embodiments, the high temperature heat pump comprises a condenser operating at a temperature greater than about 120°C. In some embodiments, the high temperature heat pump comprises a condenser operating at a temperature greater than about 150°C.
  • the present application provides a method for improving energy efficiency of a heat transfer system or apparatus comprising an incumbent refrigerant, comprising substantially replacing the incumbent refrigerant with a replacement refrigerant composition provided herein, thereby improving the efficiency of the heat transfer system.
  • the heat transfer system is a chiller system or chiller apparatus provided herein.
  • a method for operating a heat transfer system or for transferring heat that is designed to operate with an incumbent refrigerant by charging an empty system with a composition of the present invention, or by substantially replacing said incumbent refrigerant with a composition of the present invention.
  • the term “substantially replacing” shall be understood to mean allowing the incumbent refrigerant to drain from the system, or pumping the incumbent refrigerant from the system, and then charging the system with a composition of the present invention.
  • the system may be flushed with one or more quantities of the replacement refrigerant before being charged. It shall be understood that in some embodiments, some small quantity of the incumbent refrigerant may be present in the system after the system has been charged with the composition of the present invention.
  • a method for recharging a heat transfer system that contains an incumbent refrigerant and a lubricant comprising substantially removing the incumbent refrigerant from the heat transfer system while retaining a substantial portion of the lubricant in said system and introducing one of the present compositions to the heat transfer system.
  • the lubricant in the system is partially replaced.
  • the compositions of the present invention may be used to top- off a refrigerant charge in a chiller. For example, if a chiller using an incumbent refrigerant has diminished performance due to leakage of refrigerant, the compositions as disclosed herein may be added to bring performance back up to specification.
  • a heat exchange system containing any the presently disclosed compositions is provided, wherein said system is selected from the group consisting of air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, heat pumps, mobile refrigerators, mobile air conditioning units, and systems having combinations thereof.
  • the compositions provided herein may be useful in secondary loop systems wherein these compositions serve as the primary refrigerant thus providing cooling to a secondary heat transfer fluid that thereby cools a remote location.
  • the systems described herein may operate more efficiently if the heat exchangers are operated in counter-current mode or cross-current mode with counter-current tendency.
  • Counter-current tendency means that the closer the heat exchanger can get to counter-current mode the more efficient the heat transfer.
  • air conditioning heat exchangers, in particular evaporators are designed to provide some aspect of counter-current tendency.
  • the present application provides an air conditioning or heat pump system, wherein said system includes one or more heat exchangers (either evaporators, condensers or both) that operate in counter-current mode or cross-current mode with counter-current tendency.
  • heat exchangers either evaporators, condensers or both
  • a refrigeration system wherein said system includes one or more heat exchangers (either evaporators, condensers or both) that operate in counter-current mode or cross-current mode with counter-current tendency.
  • heat exchangers either evaporators, condensers or both
  • the refrigeration, air conditioning or heat pump system is a stationary refrigeration, air conditioning or heat pump system. In some embodiments the refrigeration, air conditioning, or heat pump system is a mobile refrigeration, air conditioning or heat pump system.
  • the disclosed compositions may function as primary refrigerants in secondary loop systems that provide cooling to remote locations by use of a secondary heat transfer fluid, which may comprise water, an aqueous salt solution (e.g., calcium chloride), a glycol, carbon dioxide, or a fluorinated hydrocarbon fluid (meaning an HFC, HCFC, hydrofluoroolefm (“UFO”), hydrochlorofluoroolefin (“HCFO”), chlorofluoroolefm (“CFO”), or perfluorocarbon (“PFC”).
  • the secondary heat transfer fluid is the body to be cooled as it is adjacent to the evaporator and is cooled before moving to a second remote body to be cooled.
  • the disclosed compositions may function as the secondary heat transfer fluid, thus transferring or providing cooling (or heating) to the remote location.
  • compositions provided herein further comprise one or more non-refrigerant components (also referred to herein as additives) selected from the group consisting of lubricants, dyes (including UV dyes), solubilizing agents, compatibilizers, stabilizers, tracers, anti-wear agents, extreme pressure agents, corrosion and oxidation inhibitors, polymerization inhibitors, metal surface energy reducers, metal surface deactivators, free radical scavengers, foam control agents, viscosity index improvers, pour point depressants, detergents, viscosity adjusters, and mixtures thereof.
  • non-refrigerant components also referred to herein as additives
  • additives selected from the group consisting of lubricants, dyes (including UV dyes), solubilizing agents, compatibilizers, stabilizers, tracers, anti-wear agents, extreme pressure agents, corrosion and oxidation inhibitors, polymerization inhibitors, metal surface energy reducers, metal surface deactivators, free radical scavengers, foam control
  • one or more non-refrigerant components are present in small amounts relative to the overall composition.
  • the amount of additive(s) concentration in the disclosed compositions is from less than about 0.1 weight percent to as much as about 5 weight percent of the total composition.
  • the additives are present in the disclosed compositions in an amount between about 0.1 weight percent to about 5 weight percent of the total composition or in an amount between about 0.1 weight percent to about 3.5 weight percent.
  • the additive component(s) selected for the disclosed composition is selected on the basis of the utility and/or individual equipment components or the system requirements.
  • the lubricant is selected from the group consisting of mineral oil, an alkylbenzene, a polyol ester, a polyalkylene glycol, a polyvinyl ether, a polycarbonate, a silicone, a silicate ester, a phosphate ester, a paraffin, a naphthene, a polyalpha-olefin, and combinations thereof.
  • the lubricants as disclosed herein may be commercially available lubricants.
  • the lubricant may be paraffinic mineral oil, sold by BVA Oils as BVM 100 N, naphthenic mineral oils sold by Crompton Co. under the trademarks Suniso ® 1GS,
  • Suniso ® 3GS and Suniso ® 5GS naphthenic mineral oil sold by Pennzoil under the trademark Sontex ® 372LT, naphthenic mineral oil sold by Calumet Lubricants under the trademark Calumet ® RO-30, linear alkylbenzenes sold by Shrieve Chemicals under the trademarks Zerol ® 75, Zerol ® 150 and Zerol ® 500 and branched alkylbenzene sold by Nippon Oil as HAB 22, polyol esters (POEs) sold under the trademark Castrol ® 100 by Castrol, United Kingdom, polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and mixtures thereof.
  • POGs polyalkylene glycols
  • compositions disclosed herein may acquire additional lubricant from one or more equipment components of such heat transfer system.
  • lubricants may be charged in the compressor and/or the compressor lubricant sump. Such lubricant would be in addition to any lubricant additive present in the refrigerant in such a system.
  • the refrigerant when in the compressor may pick up an amount of the equipment lubricant to change the refrigerant-lubricant composition from the starting ratio.
  • the non-refrigerant component used with the compositions of the present invention may include at least one dye.
  • the dye may be at least one ultra-violet (UV) dye.
  • UV ultra-violet
  • “ultra-violet” dye is defined as a UV fluorescent or phosphorescent composition that absorbs light in the ultra-violet or “near” ultra-violet region of the electromagnetic spectrum. The fluorescence produced by the UV fluorescent dye under illumination by a UV light that emits at least some radiation with a wavelength in the range of from 10 nanometers to about 775 nanometers may be detected.
  • UV dye is a useful component for detecting leaks of the composition by permitting one to observe the fluorescence of the dye at or in the vicinit of a leak point in an apparatus (e.g., refrigeration unit, air-conditioner or heat pump).
  • the UV emission e.g., fluorescence from the dye may be observed under an ultra-violet light. Therefore, if a composition containing such a UV dye is leaking from a given point in an apparatus, the fluorescence can be detected at the leak point, or in the vicinity of the leak point.
  • the UV dye may be a fluorescent dye.
  • the fluorescent dye is selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives of said dye, and combinations thereof.
  • Another non-refrigerant component which may be used with the compositions of the present invention may include at least one solubilizing agent selected to improve the solubility of one or more dye in the disclosed compositions.
  • the weight ratio of dye to solubilizing agent ranges from about 99:1 to about 1:1.
  • the solubilizing agents include at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (such as dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (such as methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, and 1,1,1-trifluoroalkanes and mixtures thereof.
  • hydrocarbons such as hydrocarbon ethers, polyoxyalkylene glycol ethers (such as dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (such as methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, and 1,1,1-trifluoroalkanes and mixtures thereof.
  • the non-refrigerant component comprises at least one compatibilizer to improve the compatibility of one or more lubricants with the disclosed compositions.
  • the compatibilizer may be selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (such as dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (such as methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, 1,1,1-trifluoroalkanes, and mixtures thereof, meaning mixtures of any of the compatibilizers disclosed in this paragraph.
  • the solubilizing agent and/or compatibilizer may be selected from the group consisting of hydrocarbon ethers consisting of the ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME) and mixtures thereof, meaning mixtures of any of the hydrocarbon ethers disclosed in this paragraph.
  • hydrocarbon ethers consisting of the ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME) and mixtures thereof, meaning mixtures of any of the hydrocarbon ethers disclosed in this paragraph.
  • the compatibilizer may be linear or cyclic aliphatic or aromatic hydrocarbon compatibilizer containing from 3 to 15 carbon atoms.
  • the compatibilizer may be at least one hydrocarbon, which may be selected from the group consisting of at least propanes, including propylene and propane, butanes, including n-butane and isobutene, pentanes, including n-pentane, isopentane, neopentane and cyclopentane, hexanes, octanes, nonane, and decanes, among others.
  • hydrocarbon compatibilizers include but are not limited to those from Exxon Chemical (USA) sold under the trademarks Isopar ® H, a mixture of undecane (Cn) and dodecane (C12) (a high purity Cn to C12 iso- paraffinic), Aromatic 150 (a C9 to Cn aromatic) (Aromatic 200 (a C9 to C15 aromatic) and Naptha 140 (a mixture of C5 to Cn paraffins, naphthenes and aromatic hydrocarbons) and mixtures thereof, meaning mixtures of any of the hy drocarbons disclosed in this paragraph.
  • the compatibilizer may alternatively be at least one polymeric compatibilizer.
  • R 1 , R 3 , and R 5 are independently selected from the group consisting of H and C1-C4 alkyl radicals; and R 2 , R 4 , and R 6 are independently selected from the group consisting of carbon-chain-based radicals containing C, and F, and may further contain H, Cl, ether oxygen, or sulfur in the form of thioether, sulfoxide, or sulfone groups and mixtures thereof
  • polymeric compatibilizers include those commercially available from E. I. du Pont de Nemours and Company, (Wilmington, DE, 19898, USA) under the trademark Zonyl® PHS.
  • the compatibilizer component contains from about 0.01 to 30 weight percent (based on total amount of compatibilizer) of an additive which reduces the surface energy of metallic copper, aluminum, steel, or other metals and metal alloys thereof found in heat exchangers in a way that reduces the adhesion of lubricants to the metal.
  • metal surface energy reducing additives include those commercially available from DuPont under the trademarks Zonyl ® FSA, Zonyl ® FSP, and Zonyl ® FSJ.
  • Non-refrigerant component which may be used with the compositions of the present invention may be a metal surface deactivator.
  • the metal surface deactivator is selected from the group consisting of areoxalyl bis (benzylidene) hydrazide (CAS reg no. 6629-10-3), N,N'-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine (CAS reg no. 32687-78-8), 2,2,' - oxamidobis-ethyl-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate (CAS reg no.
  • the non-refrigerant component used with the compositions of the present invention may alternatively be a stabilizer selected from the group consisting of hindered phenols, thiophosphates, butylated triphenylphosphorothionates, organo phosphates, organo phosphites, aryl alkyl ethers, terpenes, terpenoids, epoxides, fluorinated epoxides, oxetanes, ascorbic acid, thiols, lactones, thioethers, amines, nitromethane, alkylsilanes, benzophenone derivatives, aryl sulfides, divinyl terephthalic acid, diphenyl terephthalic acid, hydrazones (e.g, acetaldehyde dimethylhydrazone), ionic liquids, and mixtures thereof.
  • Terpene or terpenoid stabilizers may include farnesene
  • the stabilizer is selected from the group consisting of tocopherol, hydroquinone, t-butyl hydroquinone, monothiophosphates, and dithiophosphates, commercially available from Ciba Specialty Chemicals, Basel, Switzerland, hereinafter “Ciba”, under the trademark Irgalube ® 63; dialkylthiophosphate esters, commercially available from Ciba under the trademarks Irgalube ® 353 and Irgalube ® 350, respectively; butylated triphenylphosphorothionates, commercially available from Ciba under the trademark Irgalube ® 232; amine phosphates, commercially available from Ciba under the trademark Irgalube ® 349 (Ciba); hindered phosphites, commercially available from Ciba as Irgafos ® 168 and Tris-(di-tert-butylphenyl)phosphite, commercially
  • the compositions provide herein further comprise an ionic liquid stabilizer.
  • the ionic liquid stabilizer may be selected from the group consisting of organic salts that are liquid at room temperature (about 25°C), those salts containing cations selected from the group consisting of pyridinium, pyndazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium and triazolium and mixtures thereof ; and anions selected from the group consisting of [BF4] ,
  • ionic liquid stabilizers are selected from the group consisting of emim BF4 (1 -ethyl-3 -methylimidazoliumtetrafluoroborate); bmim BF4 (l-butyl-3- methyhmidazolium tetraborate); emim PF 6 (l-ethyl-3-methylimidazolium hexafluorophosphate); and bmim PF6 (l-butyl-3-methylimidazolium hexafluorophosphate), all of which are available from Fluka (Sigma- Aldrich).
  • the stabilizer may be a hindered phenol, which is any substituted phenol compound, including phenols comprising one or more substituted or cyclic, straight chain, or branched aliphatic substituent group, such as, alkylated monophenols including 2,6-di-tert-butyl-4-methylphenol; 2.6-di-tert-butyl -4-ethyl phenol:
  • hydroquinone and alkylated hydroquinones including t-butyl hydroquinone, other derivatives of hydroquinone; and the like, hydroxylated thiodiphenyl ethers, including 4,4’-thio-bis(2-methyl-6-tert- butylphenol); 4,4’-thiobis(3-methyl-6-tertbutylphenol); 2,2’-thiobis(4methyl-6-tert- butylphenol); and the like, alkylidene-bisphenols including,: 4,4’-methylenebis(2,6-di-tert- butylphenol); 4,4’-bis(2,6-di-tert-butylphenol); derivatives of 2,2’- or 4,4-biphenoldiols; 2,2’-methylenebis(4-ethyl-6-tertbutylphenol); 2,2’-methylenebis(4-methyl-6- tert
  • the composition provided herein further comprise a tracer.
  • the tracer may be two or more tracer compounds from the same class of compounds or from different classes of compounds.
  • the tracer is present in the compositions at a total concentration of about 50 parts per million by w eight (ppm) to about 1000 ppm, based on the weight of the total composition.
  • the tracer is present at a total concentration of about 50 ppm to about 500 ppm.
  • the tracer is present at a total concentration of about 100 ppm to about 300 ppm.
  • the tracer may be selected from the group consisting of hydro fluorocarbons (HFCs), deuterated hydrofluorocarbons, perfluorocarbons (e.g., an additional perfluorocarbon), fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes and ketones, nitrous oxide, and combinations thereof.
  • HFCs hydro fluorocarbons
  • deuterated hydrofluorocarbons e.g., an additional perfluorocarbon
  • fluoroethers e.g., brominated compounds, iodinated compounds, alcohols, aldehydes and ketones, nitrous oxide, and combinations thereof.
  • the tracer is selected from the group consisting of trifluoromethane (HFC-23), fluoroethane (HFC- 161), 1,1,1,2,2,3,3-heptafluoropropane (HFC-227ca), 1,1,1,2,2,3-hexafluoropropane (HFC-236cb), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1, 2, 2-pentafluoro propane (HFC-245cb), 1,1,2,2-tetrafluoropropane (HFC-254cb), 1,1,1,2-tetrafluoropropane (HFC- 254eb), 1,1,1-trifluoropropane (HFC-263fb), 2,2-difluoropropane (HFC-272ca), 2- fluoropropane (HFC-281ea), 1-fluoropropane (HFC-281fa), 1, 1,1, 2, 2, 3,3,4- nonafluor
  • the tracer may be added to the compositions of the present invention in predetermined quantities to allow detection of any dilution, contamination or other alteration of the composition.
  • the additive which may be used with the compositions of the present invention may alternatively be a perfluoropolyether as described in US 2007-0284555, the disclosure of which is incorporated herein by reference in its entirety.
  • the refrigerant compositions disclosed herein may be prepared by any convenient method to combine the desired amounts of the individual components as is standard in the art. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.
  • a TA Instrument RDA III Rheometer and 50mm parallel plates were used to measure the change in viscosity of the MPHE and NovecTM HFE-7200 blend from 25°C to -150°C at a frequency of lHz. A nitrogen purge was maintained around the blend during the measurement. The liquid viscosity profile as a function of temperature is shown in FIG. 2 for a blend of MPHE/HFE-7200 (70 wt%/30 wt%).
  • FIG. 1 shows a representative computer simulation of the solid-liquid equilibria of the MPHE/HFE-7200 blend over the entire composition range of the mixture.
  • the first solid of the mixture is expected to appear at -95°C and last liquid is expected to become solid at -116°C with an average freezing point of approximately - 106°C.
  • the boiling point of the 70/30 mixture is 88.3°C, and the operating temperature of the mixture is expected to be between -95°C to 69°C for single phase heat transfer fluid applications.
  • Example 2 Comparative Examples of Solid-Liquid Equilibria of MPHE and Low-
  • FIG. 3 shows results of a computer simulation of the solid-liquid equilibria performed over the entire composition range for a blend of MPHE and a lower boiling fluorinated fluid, VertrelTM XF (boiling point: 55°C).
  • the first solid of the binary mixture is expected to appear at -91.5°C and last liquid is expected to become solid at -92.5°C with an average freezing point of approximately -92°C.
  • the boiling point of the MPHE/XF mixture is 74.3°C and the expected operating temperature range is -91.5°C to 54°C.
  • FIG. 4 shows results of a computer simulation of the solid-liquid equilibria performed over the entire composition range for a blend of MPHE and a lower boiling fluorinated fluid, DR CFX70 (boiling point: 71.5°C). As shown in FIG. 3, this binary mixture did not extend the operating temperature limit when compare to pure MPHE at any composition ratio.
  • Example 3 Solid-Liquid Equilibria of HFE-7000 and HFE-7500 Blend
  • FIG. 5 shows a representative computer simulation of the solid-liquid equilibria of the HFE-7000/HFE-7500 blend over the entire composition range of the mixture.
  • a representative listing of boiling and freezing points for HFE- 7000/HFE-7500 blends is shown below in Table 2.
  • Table 3 shows the calculated liquid phase density and kinetic viscosity for a blend of MPHE and FIFE-7200 (70 wt%/30wt%), and Table 4 shows the kinetic viscosity as a function of temperature calculated for pure MPHE. Density and kinetic viscosity values were determined using computer simulation.
  • a TA Instrument RDA III Rheometer and 50mm parallel plates were used to measure the change in viscosity of the samples from 25°C to -150°C at a frequency of lHz.
  • a nitrogen purge was maintained around the blend during the measurement.
  • the freezing point of the heat transfer fluids were extrapolated based on the viscosity profile as a function of temperature.
  • Table 5 shows a comparison of the fluid freezing points calculated for pure MPHE, pure HFE-7200, a blend of 70 wt% MPHE/30 wt% HFE-7200, and a blend of 75 wt% HFE-7500/ 25wt% HFE-7000.
  • composition comprising:
  • composition of embodiment 1, wherein the composition comprises:
  • an alkyl perfluoroalkene ether (i) an alkyl perfluoroalkene ether; and (ii) a compound selected from a second hydrofluoroether, a perfluorocarbon, and a perfluoropolyether.
  • composition of embodiment 1 or 2 wherein the alkyl perfluoroalkene ether is methyl perfluoroheptene ether.
  • methyl perfluoroheptene ether comprises a mixture of about 50 weight percent 5-methoxy per(luoro-3-heptene. about 20 weight percent 3-methoxy perfluoro-3-heptene, about 20 weight percent 4- methoxy perfluoro-2-heptene, and about 8 weight percent 4-methoxy perfluoro-3- heptene.
  • composition of embodiment 3, wherein the composition comprises about 60 to about 80 weight percent methyl perfluoroheptene ether.
  • the second hydrofluoroether is selected from HFE-7000, HFE-7100, FIFE-7200, and FIFE-7500.
  • composition of any one of embodiments 1 to 6, wherein the second hydrofluoroether is FIFE-7200.
  • composition of embodiment 8 wherein the composition comprises about 40 to about 20 weight percent FIFE-7200.
  • composition of any one of embodiments 1 to 5 and 13, wherein the perfluorocarbon is FC77.
  • the composition of any one of embodiments 1 to 5, and 16, wherein the perfluoropolyether is HT110.
  • a second hydrofluoroether (ii) a second hydrofluoroether.
  • the present application further provides a process for producing cooling, comprising condensing the composition of any one of embodiments 1 to 25, and thereafter evaporating said composition in the vicinity of a body to be cooled. 27.
  • a method for producing cooling comprising circulating a heat transfer fluid comprising a composition of any one of embodiments 1 to 25, in the vicinity of a body to be cooled, wherein the heat transfer fluid is a working fluid that removes heat from, adds heat to, or maintains temperature of the vicinity of the body to be cooled.
  • the present application further provides a method of replacing heat transfer fluid in a cooling fluid distribution unit, a refrigeration system, or a heat pump system, comprising providing the composition of any one of embodiments 1 to 25, as replacement for said heat transfer fluid.
  • thermoplastic material selected from a perfluorocarbon, a perfluoropolyether, a silicon oil, a hydrocarbon oil, and an ethylene glycol aqueous solution.
  • the present application further provides a refrigeration system, comprising the composition of any one of embodiments 1 to 25.

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Abstract

La présente invention concerne des compositions (par exemple, des fluides caloporteurs) pour utilisation dans des applications de réfrigération et des applications de transfert thermique. Les compositions de la présente invention sont utiles dans des procédés de production d'un refroidissement et d'un chauffage, et des procédés de remplacement de fluides frigorigène et des appareils de réfrigération, de climatisation et de pompe à chaleur.
EP20811169.0A 2019-10-28 2020-10-27 Fluides caloporteurs pour utilisation dans des applications de refroidisseur à basse température Pending EP4051750A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201962926688P 2019-10-28 2019-10-28
PCT/US2020/057446 WO2021086804A1 (fr) 2019-10-28 2020-10-27 Fluides caloporteurs pour utilisation dans des applications de refroidisseur à basse température

Publications (1)

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EP4051750A1 true EP4051750A1 (fr) 2022-09-07

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EP20811169.0A Pending EP4051750A1 (fr) 2019-10-28 2020-10-27 Fluides caloporteurs pour utilisation dans des applications de refroidisseur à basse température

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US (1) US20230374360A1 (fr)
EP (1) EP4051750A1 (fr)
JP (1) JP2023501203A (fr)
KR (1) KR20220088762A (fr)
CN (1) CN114641552A (fr)
CA (1) CA3153966A1 (fr)
WO (1) WO2021086804A1 (fr)

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Publication number Priority date Publication date Assignee Title
CA3237827A1 (fr) * 2021-11-23 2023-06-01 The Chemours Company Fc, Llc Compositions azeotropiques et de type azeotrope de perfluoroheptene et de fluoroethers et leurs utilisations

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1981013A (zh) * 2004-01-14 2007-06-13 纳幕尔杜邦公司 氟代醚制冷剂组合物及其用途
US7220363B2 (en) * 2004-01-14 2007-05-22 E.I. Du Pont Denemours And Company 1,1,1,2,2,3,3,4,4-Nonafluoro-4-methoxybutane refrigerant compositions comprising a fluoroether and uses thereof
US7759532B2 (en) 2006-01-13 2010-07-20 E.I. Du Pont De Nemours And Company Refrigerant additive compositions containing perfluoropolyethers
US8486295B2 (en) * 2010-07-09 2013-07-16 E I Du Pont De Nemours And Company Alkyl perfluoroalkene ethers and uses thereof
TWI633179B (zh) * 2013-06-04 2018-08-21 杜邦股份有限公司 烷基全氟烯醚及其混合物於高溫熱泵的應用
CN106574215B (zh) * 2014-05-13 2018-05-25 科慕埃弗西有限公司 甲基全氟庚烯醚、1,1,1,2,2,3,4,5,5,5-十氟戊烷和反-1,2-二氯乙烯的组合物及其用途
US9840685B2 (en) * 2015-05-08 2017-12-12 The Chemours Company Fc, Llc Ternary compositions of methyl perfluoroheptene ethers and trans-1,2-dichloroethylene, and uses thereof
CA3014204C (fr) * 2016-02-25 2023-07-18 The Chemours Company Fc, Llc Utilisation de perfluoroheptenes dans des systemes a cycle de puissance
FR3052774B1 (fr) * 2016-06-16 2020-01-31 Safran Electrical & Power Melanges refrigerants faiblement inflammables ou ininflammables caracterises par une faible volatilite relative pour les systemes d'echange thermique diphasique
EP3697883A1 (fr) * 2017-10-20 2020-08-26 Dov Shellef Compositions contenant du trans-1,2-dichloroéthylène et un hydrofluoroéther, et procédés pour les utiliser
CN108823007A (zh) * 2018-06-25 2018-11-16 东阳市巍华制冷材料有限公司 一种含三氟乙基六氟丙基醚的不可燃卤代烃组合物清洁剂

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Publication number Publication date
CN114641552A (zh) 2022-06-17
CA3153966A1 (fr) 2021-05-06
WO2021086804A1 (fr) 2021-05-06
US20230374360A1 (en) 2023-11-23
JP2023501203A (ja) 2023-01-18
KR20220088762A (ko) 2022-06-28

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